Dried allulose crystals

ABSTRACT

The teachings herein relate to dried allulose crystals having low water content. The water content of the dried allulose crystals may be at most 0.1 weight percent. Preferably, the water content is at most 0.01 weight percent and more preferably at most 0.001 weight percent. The dried allulose crystals preferably are free flowing. The dried allulose crystals preferably have reduced hygroscopicity and/or improved sensory properties.

PRIORITY

The present application a continuation of U.S. patent application Ser.No. 17/529,841 filed on Nov. 18, 2021, which claims priority to EuropeanPatent Application number 20209177.3 filed on Nov. 23, 2020. Thisapplication claims priority to U.S. patent application Ser. No.17/529,841 and European Patent Application 20209177.3, and incorporatesU.S. patent application Ser. No. 17/529,841 by reference in itsentirety.

FIELD OF THE INVENTION

The invention is in the field of food technology and relates to aprocess for drying allulose crystals.

TECHNOLOGICAL BACKGROUND

Allulose (Psicose) is a low-calorie sugar with similar sweet taste ofsugar. Allulose is one of many different sugars found in nature in verysmall amounts. Allulose was originally identified from wheat and hassince been found in certain fruits such as jackfruit, figs and raisins.Allulose is naturally found in small amounts in a variety of sweet foodssuch as caramel sauce, maple syrup and brown sugar. Allulose is absorbedbut not metabolized by the body, making it virtually calorie-free.

Due to the growing interest of a large portion of the population in“healthy eating” and “healthy living” in general, allulose has attracteda great deal of interest in the food industry and scientific communityas a calorie-free sugar.

Allulose is often commercialized in the form of crystals.

RELEVANT STATE OF THE ART

Processes for the preparation of allulose in crystalline form are knownin the prior art. For example, document EP 2 552 241 B1 (CJ CHEILJEDANGCORP) discloses a process for producing D-psicose comprising thefollowing steps: (a) removing impurities from a D-psicose solution toobtain a purified D-psicose solution, (b) concentrating the purifiedD-psicose solution at a temperature of 60° C. to 70° C., and (c)crystallizing the D-psicose from the concentrated D-psicose solution ina super-saturated state under a metastable zone. The process comprisesrecovering the D-psicose crystals obtained during crystallization, andwashing the crystals with deionized water and drying the crystals.Drying of the crystals can be performed in a fluidized bed dryer or avacuum dryer.

However, producers of allulose in crystalline form are faced with theproblem that the dried allulose crystals reabsorb moisture very quickly,depending on the drying method. This hygroscopicity of dried allulosecrystals causes not only difficulties in handling, but also a reductionin the storage stability of the product.

Therefore, there is a strong need in the field of food technology forenergy-saving processes that allow improved drying of high-qualityallulose crystals.

TASK OF THE INVENTION

The task of the present invention has thus been to provide a process fordrying allulose crystals which are free from the disadvantages describedat the outset. In particular, the allulose crystals obtained should havea low hygroscopicity.

Thus, a second object of the present invention has been to provide amethod for drying allulose crystals such that the obtained allulosecrystals are free-flowing, readily soluble in water and have a goodtaste.

DESCRIPTION OF THE INVENTION

It is an object of the present invention to provide a process for dryingallulose crystals comprising or consisting of the following steps:

-   -   (a) providing non-dried allulose crystals,    -   (b) temperature-treating the crystals according to step (a) at a        temperature in the range of about 25 to about 70° C. in a drying        apparatus, wherein the temperature treatment is carried out        -   (b1) at atmospheric pressure and a residence time in the            range of about 5 minutes to about 5 hours, or        -   (b2) under reduced pressure and constant temperature and a            residence time ranging from about 30 min to 5 hours, and    -   (c) conditioning the intermediate product obtained in step (b1)        or (b2), wherein conditioning is carried out        -   (c1) over a period of about 30 min to 7 hours at a            temperature in the range of about 40 to about 70° C., or        -   (c2) over a period of about 15 to 90 hours with air of a            relative humidity of about 30 to about 60% and at a            temperature of about 25 to about 40° C.

Surprisingly, it was found that allulose crystals dried by the method ofthe invention present a free-flowing product, and have a considerablylower hygroscopicity than allulose crystals dried by the standardconditions. Accordingly, the obtained allulose crystals arecharacterized by considerable storage stability.

Furthermore, it was surprisingly found that allulose crystals dried bymeans of the process according to the invention are in particular easilysoluble and sensorially perfect.

Allulose, also known as psicose, is a ketohexose. For the purposes ofthe present invention, allulose is preferably provided in the form ofthe D-enantiomer, i.e. D-allulose (CAS No. 551-68-8). D-allulose may bein the form of various anomers such as α-D-allulose and β-D-allulose.

For the purposes of the present invention, the term “temperaturetreatment” of step (b) should also be understood as “drying” or“tempering.”

For the purposes of the present invention, the term “conditioning” isalso to be understood as a “post-crystallization” which is carried outin the absence of a solvent. That is, the intermediates obtained insteps (b1) or (b2) are not brought into contact with a solvent duringstep (c).

In terms of the present invention, the process used to produce thenon-dried allulose crystals according to step (a) is not critical forthe successful performance of the drying process according to theinvention.

However, in a preferred embodiment, the non-dried allulose crystalsaccording to step (a) have a purity greater than 95%, preferably greaterthan 98%, and more preferably in the range of 98.5 to 99.5%—in each casebased on the total dry mass.

In a preferred embodiment of the drying process according to theinvention, at least 10% by weight, at least 20% by weight, at least 30%by weight, at least 40% by weight, at least 50% by weight, at least 60%by weight, at least 70% by weight, at least 80% by weight, at least 90%by weight, at least 95% by weight, or at least 98% by weight, at least99 wt. % of the allulose in the non-dried allulose crystals of step (a)is present in the form of β-D-psicopyranose—in each case again based onthe total dry weight.

In the sense of the present invention, the non-dried allulose crystalsof step (a) are obtained from a concentrated allulose suspension bymeans of separation, in particular by means of centrifugation orfiltration, from the mother liquor.

In a preferred embodiment, the non-dried allulose crystals according tostep (a) have a water content of at most about 40% by weight at most,preferably of about 35% by weight at most, preferably of about 30% byweight at most, preferably of about 25% by weight at most, preferably ofabout 20% by weight at most, preferably of about 15% by weight at most,preferably of about 10% by weight at most, preferably of about 9% byweight at most, preferably of about 8% by weight at most. %, preferablyof at most about 7% by weight, preferably of at most about 6% by weight,preferably of at most about 5% by weight, preferably of at most about 4%by weight, preferably of at most about 3% by weight, preferably of atmost about 2% by weight, preferably of at most about 1% by weight, andpreferably of at most about 0.5% by weight.

In another preferred embodiment, the non-dried allulose crystalsaccording to step (a) have a water content of about 10-0.3 wt.-%,preferably of about 8-0.4 wt.-%, and more preferably of about 5-0.5wt.-%.

As mentioned above, the non-dried allulose crystals according to step(a) are subjected to a temperature treatment in a drying plant. Thetemperature treatment according to step (b)—in both variant (b1) andvariant (b2)—is carried out at a temperature in the range from about 25to about 70° C.

In a preferred embodiment, the temperature treatment of step (b) iscarried out at a temperature in the range from about 30 to about 65° C.and, in particular, preferably in the range from about 30 to about 60°C.

In terms of the present invention, various drying systems are suitablefor cars tying out the temperature treatment according to step (b), forexample, drum dryers, belt dryers, shaft dryers, conical dryers,convection dryers, vibrating fluidized bed dryers, fluidized bed dryers,tube bundle dryers, thin layer dryers, disc dryers, vacuum dryers,contact dryers and microwave dryers. These drying systems are well knownto those skilled in the art and therefore need not be explained indetail.

However, carrying out the temperature treatment according to step (b) ina drying plant selected from the group consisting of fluidized bed dryer(continuous), vacuum dryer, belt dryer and thin film dryer, inparticular fluidized bed dryer and vacuum dryer, has proven to beparticularly advantageous.

According to the invention, the temperature treatment can be carried outeither by means of variant (b1) or by means of variant (b2).

As mentioned above, the temperature treatment according to (b1) iscarried out at atmospheric pressure and a residence time in the dryingsystem in the range of about 5 minutes to about 5 hours.

In a preferred embodiment, the temperature treatment according to (b1)is carried out at a constant temperature (which of course falls withinthe range defined in (b)).

In another preferred embodiment, the drying system in (b1) has differentheating zones. The different heating zones are the individuallycontrollable, so that it is possible to create an arbitrary temperatureprofile.

In a preferred embodiment, the drying system in (b1) has 2 to 5different heating zones. Each heating zone has a different temperature,with the temperatures of each heating zone naturally falling within therange defined in (b); non-adjacent heating zones may have the sametemperature. In a preferred embodiment, the dwell time per heating zoneof the drying system is about 1 to about 8 minutes, preferably about 3to about 8 minutes, more preferably about 4 to about 7 minutes.

It has been found to be particularly advantageous in terms of energy ifthe drying system has three different heating zones in step (b1). In apreferred embodiment, the temperature profile corresponds to thefollowing scheme:

-   -   T1 _(Heating zone)<T2 _(Heating zone)>T3 _(Heating zone), where        T1 _(Heating zone)≥T3 _(Heating zone)    -   or    -   T1 _(Heating zone)<T2 _(Heating zone)>T3 _(Heating zone), where        T1 _(Heating zone)≤T3 _(Heating zone)

In a preferred embodiment, the temperatures in the 3 different heatingzones are set as follows:

-   -   T1 _(Heating zone) is in the range of 30-45° C., preferably,        35-40° C., and more preferably 40° C.;    -   T2 _(Heating zone) is in the range of 50-70° C., preferably,        55-65° C., and more preferably 60° C.;    -   T3 _(Heating zone) is in the range of 25-35° C., preferably,        25-30° C., and more preferably 30° C.

In a preferred embodiment, if the drying system has three differentheating zones, the residence time per heating zone of the drying systemis about 3 to 8 minutes, preferably 4 to 6 minutes, and more preferably4 minutes.

As mentioned above, the temperature treatment according to (b2) iscarried out under reduced pressure and constant temperature (which ofcourse falls within the range defined in (b)) and a residence time inthe drying plant of about 30 min to 5 hours.

In a preferred embodiment, the temperature treatment according to step(b2) is carried out at a pressure of from about 5 to about 300 mbar,preferably from about 10 to about 250 mbar and particularly preferablyat a pressure of from about 20 to about 200 mbar.

In a preferred embodiment, the temperature treatment according to step(b2) is carried out at a temperature in the range from about 25 to about45° C., preferably from about 30 to about 40° C., and particularlypreferably from about 30 to about 35° C.

In another preferred embodiment, the residence time in the drying systemis from about 1 to about 4 hours, preferably from about 2 to about 4hours, and more preferably about 3 hours.

In a particularly preferred embodiment, the temperature treatmentaccording to step (b2) is carried out at a pressure of about 20 to about200 mbar and a temperature of about 30 to about 40° C. and a residencetime in the drying plant of about 3 hours.

The water content of the intermediate product obtained in step (b1) or(b2) is in the range of from about 0.1 to about 0.5 wt.-%, preferablyfrom about 0.1 to about 0.3 wt.-%, more preferably from about 0.15 to0.25 wt.-%.

Although the intermediate product obtained in step (b1) or (b2) has asignificantly reduced water content compared to the non-dried allulosecrystals of step (a), the properties of this intermediate product arenot satisfactory, especially with respect to the pourability of theproduct.

According to the invention, after the temperature treatment,conditioning of the intermediate product obtained in step (b1) or (b2)is carried out. By this is meant storing the intermediates obtained instep (b1) or (b2) for a certain period of time at a certain temperatureor in contact with an air having specific properties with respect towater loading, so that a kind of “post-crystallization” takes place.

In the sense of the present invention, various devices for carrying outthe conditioning according to step (c)—both in variant (c1) and invariant (c2)—can be considered, for example drum dryers, belt dryers,shaft dryer, conical dryer, convection dryer, vibrating fluidized beddryer, fluidized bed dryer, tube bundle dryer, thin layer dryer, discdryer, vacuum dryer, big bags, or conveyor system for pneumaticconveying (e.g., in a silo). These drying systems are well known tothose skilled in the art and therefore need not be explained in detail.

In a preferred embodiment, the conditioning according to step (c) iscarried out in a device selected from the group consisting of a drumdryer, fluid bed dryer, vacuum dryer, thin layer dryer, or a conveyorsystem for pneumatic conveying (e.g., in a silo).

In terms of the present invention, performing the conditioning does notnecessarily require transferring the intermediate product according to(b1) or (b2) from a first apparatus where the temperature treatment wasperformed to a second apparatus where the conditioning is to beperformed. It is quite possible to carry out steps (b) and (c) in theirrespective variants in the same device. For example, a temperaturetreatment according to (b2) can be performed in a vacuum dryer, and theconditioning can be performed in the same vacuum dryer.

In a first variant (c1), the conditioning is performed over a period ofabout 30 minutes to 7 hours at a temperature in the range of about 40 toabout 70° C.

In a preferred embodiment, the conditioning according to (c1) is carriedout at a temperature in the range of about 50 to about 70° C.,preferably in the range of about 55 to about 65° C., more preferably inthe range of about 58 to about 62° C.

In a further preferred embodiment, the conditioning according to (c1) iscarried out over a period of about 30 minutes to 6 hours at atemperature >50° C.

In a very particular preferred embodiment, the conditioning according to(c1) is carried out over a period of time of about 3 to 6 hours at atemperature of about 60° C.

In variant (c2), the conditioning is carried out over a period of about15 to about 90 hours with air of a relative humidity of about 30 toabout 60% and at a temperature of about 25 to about 40° C.

In a preferred embodiment, the conditioning according to (c2) is carriedout over a period of about 24 to about 72 hours and air to a temperatureof about 30 to about 35° C., preferably 30° C.

In a further embodiment, the conditioning according to (c2) is carriedout with air from a relative humidity of about 35 to about 55%,preferably from about 35 to about 45%, and particularly preferably about40 to about 45%.

In a particularly preferred embodiment, the conditioning according to(c2) is carried out over a period of about 24 to about 72 hours and withair of a relative humidity of about 40% and to a temperature of about30° C.

In another preferred embodiment, the conditioning according to (c2) iscarried out in a thin film dryer, wherein the distributed intermediateproduct from the temperature treatment has a film thickness <10 mm.

The dried allulose crystals obtained by means of the process accordingto the invention have a water content of at most 0.1% by weight,preferably of at most 0.01% by weight, and particularly preferably of atmost 0.001% by weight.

Accordingly, it is also an object of the present invention to provideallulose crystals having a content of water of at most 0.001% by weight,wherein the dried allulose crystals are produced by means of the processdescribed above.

In summary, the process according to the invention allows obtaining highquality allulose crystals which are free-flowing and characterized byexcellent solubility, low hygroscopicity and excellent sensoryproperties.

EXAMPLES

The present invention will be more readily understood with reference tothe examples below.

However, these examples are merely illustrative of the invention andcannot be construed as limiting the scope of protection of theinvention.

Comparative Example C1

Allulose crystals were obtained by centrifugation from the mother liquorfrom a concentrated allulose suspension (content of allulose in totaldry matter of 97% by weight). The separated allulose crystals were thendried for 24 hours in a vacuum drying oven at 30° C. and a pressure of10 mbar. A product was obtained which had a purity of 98% and a watercontent of 0.15 wt.-%. It was found that the product was highlyhygroscopic and non-free-flowing.

Example 1 (According to the Invention)

Allulose crystals were obtained by centrifugation from the mother liquorfrom a concentrated allulose suspension (content of allulose in totaldry matter of 97 wt.-%). The separated allulose crystals were subjectedto temperature treatment in a continuous fluid bed dryer. The fluid beddryer had three heating zones, where.

-   -   T1 _(Heating zone)=40° C.,    -   T2 _(Heating zone)=60° C., and    -   T3 _(Heating zone)=30° C.

The residence time per heating zone of the fluid bed dryer was 4 minuteseach. The intermediate product obtained had a residual water content of0.2 wt. %, and was not free-flowing. Subsequently, this intermediate wassubjected to conditioning in a rotating drying drum for 3 hours and at atemperature of 60° C. The allulose crystals thus obtained had a maximumwater content of 0.07 wt. %. The allulose crystals thus obtainedconstituted a free-flowing product.

Example 2 (According to the Invention)

Allulose crystals were obtained by centrifugation from the mother liquorfrom a concentrated allulose suspension (content of allulose in totaldry matter of 97 wt.-%). The separated allulose crystals were subjectedto temperature treatment in a continuous fluidized bed dryer for 30minutes at a temperature of 60° C. The obtained intermediate had aresidual water content of 0.2 wt.-%, and was not free-flowing.Subsequently, this intermediate was subjected to conditioning in acontinuous fluid bed dryer for 3 hours and at a temperature of 60° C.The allulose crystals thus obtained had a maximum water content of 0.08wt. %. The allulose crystals thus obtained constituted a free-flowingproduct.

Example 3 (According to the Invention)

Allulose crystals were obtained by centrifugation from the mother liquorfrom a concentrated allulose suspension (content of allulose in totaldry matter of 97 wt.-%). The separated allulose crystals were subjectedto temperature treatment in a vacuum dryer for 3 hours at a temperatureof 30° C. and a pressure of 150 mbar. The obtained intermediate had aresidual water content of 0.2 wt.-%, and was not free-flowing.Subsequently, this intermediate was subjected to conditioning in athin-layer dryer for 24 h with air at 25° C. with a water loading of 40%(corresponding to 8.0 g of water per kg of dry air). The allulosecrystals thus obtained had a maximum water content of 0.1% by weight.The allulose crystals thus obtained constituted a free-flowing product.

Example 4 (According to the Invention)

Allulose crystals were obtained by centrifugation from the mother liquorfrom a concentrated allulose suspension (content of allulose in totaldry matter of 97 wt.-%). The separated allulose crystals were subjectedto temperature treatment in a vacuum dryer for 3 hours at a temperatureof 30° C. and a pressure of 150 mbar. The obtained intermediate had aresidual water content of 0.2 wt.-% and was not free-flowing. Subsequentconditioning was carried out by circulating the product by pneumaticconveying in a silo (4 hours at 60° C.). The allulose crystals thusobtained had a maximum water content of 0.001 wt.-%. The allulosecrystals thus obtained represented a free-flowing product.

Evaluation of the Crystals

The solubility in water (g/liter), the increase in water content, andthe sensory properties were evaluated after storage of the obtainedallulose crystals in an open vessel for 24 hours by a panel consistingof five experienced and trained testers (3=pronounced, 2=present, 1=notto be determined). The results are summarized in Table 1.

TABLE 1 Solubility, sensory index and increase in water content afterstorage of dried crystals in an open container for 24 hours. SolubilitySensory (mean Increase in water Examples index (ml) value) content (%) 1<0.1 1 <0.1 2 <0.1 1 <0.1 3 <0.1 1 <0.1 4 <0.1 1 <0.1 C1 <0.2 2 >0.2

The experimental data show that the allulose crystals dried by themethod of the invention exhibit improved results in terms of solubilityand sensory properties.

Moreover, the allulose crystals dried by means of the process accordingto the invention, are those for which the lowest increase in watercontent was obtained after storage for 24 hours in an open vessel.

1-14. (canceled)
 15. Allulose crystals having a water content of at most0.1 weight percent.
 16. The allulose crystals of claim 15, wherein thewater content is at most 0.01 weight percent.
 17. The allulose crystalsof claim 15, wherein the water content is at most 0.001 weight percent.18. The allulose crystals of claim 15, wherein the allulose crystalshave a purity of greater than 95 percent.
 19. The allulose crystals ofclaim 15, wherein the allulose crystals have a purity of greater than 98percent.
 20. The allulose crystals of claim 15, wherein the allulosecrystals have a purity of 98.5 percent to 99.5 percent.
 21. The allulosecrystals of claim 15, wherein an increase in the water content of theallulose crystals is less than 0.1 percent after 24 hours in an opencontainer.
 22. The allulose crystals of claim 15, wherein the allulosecrystals have an improved sensory property compared to allulose crystalshaving a water content of 0.15 weight percent and a purity of 98 weightpercent.
 23. The allulose crystals of claim 15, wherein the allulosecrystals are free flowing.
 24. The allulose crystals of claim 15,wherein the allulose crystals have a purity of greater than 95 percent,and an increase in the water content of the allulose crystals is lessthan 0.1 percent after 24 hours in an open container.
 25. The allulosecrystals of claim 24, wherein the allulose crystals are free flowing.26. The allulose crystals of claim 25, wherein the water content is atmost 0.01 weight percent.
 27. The allulose crystals of claim 26, whereinthe allulose crystals have a purity of greater than 98 percent.
 28. Theallulose crystals of claim 27, wherein the allulose crystals have apurity of 98.5 percent to 99.5 percent and wherein the water content isat most 0.001 weight percent.
 29. The allulose crystals of claim 15,wherein the allulose crystals have a purity of greater than 98 percentand wherein the water content is at most 0.01 weight percent.
 30. Theallulose crystals of claim 15, wherein the allulose crystals have apurity of 98.5 percent to 99.5 percent and wherein the water content isat most 0.001 weight percent.
 31. The allulose crystals of claim 15,wherein the allulose crystals are prepared by a process comprising stepsof: (a) providing non-dried allulose crystals, (b) temperature treatingthe crystals according to step (a) at a temperature in the range ofabout 25 to about 70° C. in a drying apparatus, wherein the temperaturetreatment is carried out (b1) at atmospheric pressure and a residencetime in the range of about 5 minutes to about 5 hours, or (b2) underreduced pressure and constant temperature and a residence time rangingfrom about 30 min to 5 hours, and (c) conditioning the intermediateproduct obtained in step (b1) or (b2), wherein conditioning is carriedout (c1) over a period of about 30 min to 7 hours at a temperature inthe range of about 40 to about 70° C., or (c2) over a period of about 15to about 90 hours with air of a relative humidity of about 30 to about60% and at a temperature of about 25 to about 40° C.
 32. The allulosecrystals of claim 31, wherein the allulose crystals have an improvedsensory property.
 33. The allulose crystals of claim 31, wherein theallulose crystals have an improved sensory property compared to allulosecrystals having a water content of 0.15 weight percent and a purity of98 weight percent.